Glass fiber forming compositions

ABSTRACT

A glass fiber composition has 52 to 62 percent by weight SiO 2 , 0 to 2 percent by weight NaO 2 O, 16 to 25 percent by weight CaO, 8 to 16 percent by weight Al 2 O 3 , 0.05 to 0.80 percent by weight Fe 2 O 3 , 0 to 2 percent by weight K 2 , 1 to 5 percent by weight MgO, 0 to 5 percent by weight B 2 O 3 , to 0 to 2 percent by weight TiO 2 , and 0 to 1 percent by weight F, and further has a log 3 forming temperature of no greater than 1240° C. based on an NIST 714 reference standard, a ΔT of at least 50° C., and a SiO 2 /RO ratio of no greater than 2.35.

CROSS REFERENCE TO RELATED PATENT APPLICATIONS

This application claims the benefit of U.S. Provisional Application No. 60/230,474, filed Sep. 6, 2000.

The present invention relates to glass compositions for making glass fibers, and more particular to glass compositions having lowered liquidus and forming temperatures.

The most common glass composition for making continuous glass fiber strands for textiles and glass fiber reinforcements is “E” glass. The requirements as to what type of composition constitutes an E-glass composition are included in ASTM D578-98. An advantage of using E-glass is that its liquidus temperature is well below its forming temperature, i.e. typically greater than 56° C. (100° F.) and generally between 83 to 111° C. (150 to 200° F.). As used herein, the terms “forming temperature”, “T_(FORM)” and “log 3 forming temperature” mean the temperature of the glass at which the viscosity of the glass is log 3, or 1000 poise, and the terms “liquidus temperature” and “T_(LIQ)” mean the temperature at which solid phase (crystals) and liquid phase (melt) are in equilibrium. The difference between T_(FORM) and T_(LIQ), referred to herein as “delta T” or “ΔT”, is a common measure of the crystallization potential of a given melt composition. In the glass fiber forming industry, ΔT is typically maintained at a temperature of at least 50° C. (90° F.) in order to prevent devitrification of the molten glass during a glass fiber forming operation, and in particular in the bushing area.

Boron and fluorine containing glass were developed to meet these operating conditions. More specifically, the boron and fluorine were included in the glass batch materials to act as fluxes during the glass melting operation. In particular, E-glass can include up to 10 wt % B₂O₃ and up to 1.0 fluoride (see ASTM D 578-00 §4.2). However, these materials are volatilized during melting and boron and fluorine emissions are released to the atmosphere. Since boron and fluorine are considered pollutants, these emissions are closely controlled by environmental regulations, which in turn requires careful control of the furnace operations and the use of expensive pollution control equipment. In response to this, low boron and/or low fluorine E-glasses were developed. As used herein, “low boron” means that the glass composition is no greater than 5 weight percent (wt %) boron, and includes boron-free glass, and “low fluorine” means that the glass composition is no greater than 0.30 wt % fluorine, and includes fluorine-free glass.

For additional information concerning glass compositions and methods for fiberizing the glass composition, see K. Loewenstein, The Manufacturing Technology of Continuous Glass Fibres, (3d Ed. 1993) at pages 30-44, 47-60, 115-122 and 126-135, and F. T. Wallenberger (editor), Advanced Inorganic Fibers: Processes, Structures, Properties, Applications, (2000) at pages 81-102 and 129-168, which are hereby incorporated by reference.

Because the actual glass fiber forming operation is conducted at high temperatures, there is high energy usage associated with its production, along with associated high energy costs. In addition, the high temperatures accelerate the degradation of the refractory used in the glass melting furnace, as well as the bushings used to form the fibers. The bushings include precious metals that cannot be recovered from the glass as the bushings corrode. It would be advantageous to produce the glass fibers at the lowest possible forming and liquidus temperatures so as to reduce the energy usage and costs and thermal load on the furnace refractory and bushings, while at the same time provide the ΔT required to ensure an uninterrupted glass fiber forming operation. Reducing the forming and liquidus temperatures of the glass compositions can also result in environmental benefits, such as but not limited to, a reduction in the amount of fuel required to generate the energy necessary for the fiber forming operation, as well as a reduction in the flue gas temperature. In addition, it would be advantageous if the glass compositions are low fluorine and/or low boron compositions so as to reduce or eliminate the environmental pollutants associated with these materials.

The present invention provides a low boron content glass fiber forming composition that has a forming temperature of no greater than 1240° C. (2262° F.), a ΔT of at least 50° C. (90° F.), and a ratio of SiO₂ to RO (i.e. CaO+MgO) of no greater than 2.35. In one nonlimiting embodiment of the present invention, the glass composition has a silica content of no greater than 59 weight percent. In another nonlimiting embodiment of the invention, the glass composition is boron-free.

The foregoing summary, as well as the following detailed description of embodiments of the present invention, will be better understood when read in conjunction with the appended drawings. In the drawings:

FIGS. 1-6 are curves showing the relationship between the ratio of SiO₂ to RO of various glass fiber forming compositions to the compositions' forming and liquidus temperatures based on the data shown in corresponding Tables A through F, respectively.

The base composition for the low boron glass fibers of the present invention suitable for textiles and glass fiber reinforcements includes the following main constituents in weight percent based on the total weight of the final glass composition.

broad alternate range range SiO₂ (wt %)   52 to 62 53 to 59 Na₂O (wt %)   0 to 2 up to 1.5 CaO (wt %)   16 to 25 20 to 25 Al₂O₃ (wt %)   8 to 16 11 to 14 Fe₂O₃ (wt %) 0.05 to 0.80 up to 0.5 K₂O (wt %)   0 to 2 up to 1

It should be appreciated that, unless otherwise indicated, all numerical values discussed herein, such as but not limited to weight percent of materials or temperatures, are approximate and are subject to variations due to various factors well known to those skilled in the art such as, but not limited to, measurement standards, equipment and techniques. As a result, such values are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. For example, where it states in the present application that the range for SiO₂ is 52 to 62 weight percent, this range is about 52 to about 62 weight percent, and where it states that the forming temperature of a glass composition should be no greater than 1249° C. (2280° F.), the temperature is about 1249° C.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

In addition, where the amount of a particular material or combinations of materials disclosed herein is expressed in terms of “percent” or “%”, it should be understood that this means “weight percent” or “wt %”.

Additional materials can be added to the glass composition to modify the melt properties of the glass. For example, and without limiting the glass compositions disclosed herein, Li₂O, ZnO, MnO and/or MnO₂, can be added to the glass fiber composition to reduce T_(FORM) and/or T_(LIQ). In one non-limiting embodiment of the present invention, the glass composition includes 0 to 1.5 wt % Li₂O and/or 0 to 1.5 wt % ZnO and/or 0 to 3 wt % MnO and/or 0 to 3 wt % MnO₂. It is believed that levels of these materials less than 0.05 wt % would be considered either tramp amounts or so low that they will not materially impact the glass melt properties. As a result, in another non-limiting embodiment, 0.05 to 1.5 wt % Li₂O and/or 0.05 to 1.5 wt % ZnO and/or 0.05 to 3 wt % MnO and/or 0.05 to 3 wt % MnO₂ are included in the glass composition. In still another nonlimiting embodiment of the invention, the glass compositions include 0.2 to 1 wt % Li₂O and/or 0.2 to 1 wt % ZnO and/or up to 1 wt % MnO and/or up to 1 wt % MnO₂.

MgO is another material typically included in a glass fiber forming composition. It has been found that the heating and melting profile of a glass fiber composition, and in particular the liquidus temperature, can be controlled and in particular optimized by controlling the amount of MgO. In addition, it has been determined that a eutectic (minimum liquidus temperature) exists in a generic quaternary SiO₂—Al₂O₃—CaO—MgO at around 2.5 wt % MgO (see PCT Application No. US 00/14155, which is incorporated herein by reference). Without limiting the present invention, in one nonlimiting embodiment, the glass fiber composition includes 1 to 5 wt % MgO, e.g. 1 to 4 wt % or 1.7 to 2.9 wt % or 1.9 to 2.65 wt % MgO.

Boron is another material that can be added to glass fiber compositions to reduce T_(FORM) and T_(LIQ). However, as discussed earlier, the inclusion of boron results in the production of particulate emissions that, depending on the particulate level, may have to be removed from a melting furnace exhaust stream before being released into the environment. Although the amount of B₂O₃ in a glass fiber composition can be as high as 10 wt %, in the present invention, the glass composition has a low boron content, i.e. has a B₂O₃ content of no greater than 5 wt %. In other nonlimiting embodiments of the present invention, the glass fiber composition has no greater than 4 wt %, or no greater than 3 wt %, or no greater than 2 wt % B₂O₃. In another nonlimiting embodiment of a glass fiber forming composition, the low boron content glass composition is essentially boron-free, i.e. it includes no more than a trace amount of B₂O₃, which is considered herein to be up to 0.05 wt % B₂O₃. In still another nonlimiting embodiment, the low boron content glass fiber composition does not include any B₂O₃.

It should be appreciated that glass fiber compositions can include other constituents and the present invention contemplates the inclusion of other materials in the glass fiber compositions, such as, but not limited to, 0 to 2 wt % each of TiO₂, BaO, ZrO₂ and SrO, e.g. up to 1.5 wt % or up to 1 wt % of each of these materials.

In addition, because of the environmental concerns discussed earlier, in one nonlimiting embodiment of the present invention, the glass composition has a low fluorine content. In another nonlimiting embodiment, the glass composition is fluorine-free, i.e. it includes no more than a trace amount of fluorine, which is considered herein to be up to 0.05 wt % fluorine. In still another nonlimiting embodiment, the glass composition does not include any fluorine. Except where otherwise indicated, the glass fiber forming compositions disclosed and discussed herein are fluorine-free.

It should be appreciated that the glass compositions disclosed herein can also include small amounts of other materials, for example melting and refining aids, tramp materials or impurities. For example and without limiting the present invention, melting and fining aids, such as SO₃, are useful during production of the glass, but their residual amounts in the glass can vary and have minimal, if any, material effect on the properties of the glass product. In addition, small amounts of the additives discussed above can enter the glass composition as tramp materials or impurities included in the raw materials of the main constituents.

Commercial glass fibers of the present invention can be prepared in the conventional manner well known in the art, by blending the raw materials used to supply the specific oxides that form the composition of the fibers. For example, typically sand is used for SiO₂, clay for Al₂O₃, lime or limestone for CaO, and dolomite for MgO and some of the CaO. As discussed earlier, the glass can include other additives that are added to modify the glass properties as well as small amounts of melting and refining aids, tramp materials or impurities.

After the ingredients are mixed in the proper proportions to provide the desired weight of each constituent for the desired glass, the batch is melted in a conventional glass fiber melting furnace and the resulting molten glass is passed along a conventional forehearth and into a glass fiber forming bushing located along the bottom of the forehearth, as is well known to those skilled in the art. During the glass melting phase, the glass batch materials are typically heated to a temperature of at least 1400° C. (2550° F.). The molten glass is then drawn or pulled through a plurality of holes in the bottom of the bushing. The streams of molten glass are attenuated to form filaments by gathering a plurality of filaments together to form a strand and winding the strand on a forming tube mounted on a rotatable collet of a winding machine. Alternatively, the fiber forming apparatus can be, for example, a forming device for synthetic textile fibers or strands in which fibers are drawn from nozzles, for example a spinneret, wherein fibers are drawn through holes in a plate, as is known to those skilled in the art. Typical forehearths and glass fiber forming arrangements are shown in K. Loewenstein, The Manufacturing Technology of Continuous Glass Fibres, (Third Edition 1993) at pages 85-107 and pages 115-135, which are hereby incorporated by reference.

Several series of different types of low boron glass fiber compositions were made to examine certain relationships between the amount of selected glass constituents and the corresponding forming and liquidus temperatures in order to identify glass compositions having a lowered forming temperature and a desired ΔT. During testing, the glass compositions for the different series of experimental samples were divided into the following main compositional categories and subcategories:

Type I-high T_(Form) (T_(form>)1240° C.), low boron content

Type I-1 boron-free

Type I-2 up to 2.5 wt % B₂O₃

Type II-low T_(form) (T_(form)≦1240° C.) low boron content, 2.5 wt % MgO

Type II-1 boron-free

Type II-2 up to 5 wt % B₂O₃

Type III-low T_(form) (T_(form)≦1240° C.) low boron content, 2.5 wt % MgO lithium and/or zinc

Type III-1 boron-free with lithium

Type III-2 boron-free with lithium and zinc

Type III-3 boron-free with zinc

Type III-4 up to 5% wt % B₂O₃with lithium

Type I-1 glasses would include prior art glasses such as those disclosed in Example 1 of French Patent 2,768,144 (hereafter “Patent '144”) U.S. Pat. Nos. 4,542,106 and 5,789,329 (hereafter “Patent '106”and “Patent '329”, respectively), and ADVANTEX® glass, which is commercially available from Owens Coming Fiberglass, and typically include approximately 60 wt % SiO₂, 25 wt % CaO+MgO (hereinafter “RO”), and 12-14 wt % Al₂O₃ and are boron-free. Type I-2 glasses would include prior art glasses such as that disclaosed in Example 2 Patent '144, which includes 1.8 wt % B₂O₃ and 60.82 wt % SiO₂.

tables A through F include examples of each series of glass fiber compositions and were used to generate corresponding FIGS. 1-6, respectively, as will be discussed late in more detail. In Table A, Examples 1-8are Type II-1 glasses while Examples 9-34 are Type I-1 glasses In Table B, Examples 35-77 are Type II-2 glasses while Examples 78-83 are Type I-2 glasses. In Table C, Examples 84-143 and 152-156 are Type III-1 glasses while Examples 144-151 are similar but have a log 3 forming temperature greater than 1240° C. In Table D, Examples 157-171 are Type III-2 glasses while Examples 172-183 are Type III-3 glasses while Examples 184-193 are similar but have a log 3 forming temperature greater than 1240° C. In Table F, Examples 198-296 are Type III-4 glasses while Examples 297 and 298 are similar but have a log 3 forming temperature greater than 1240° C.

TABLE A TYPE I-1 AND II-1 GLASS Composition Examples Weight % 1 2 3 4 5 6 7 8 9 10 SiO2 57.95 57.75 58.05 57.65 57.45 58.72 57.72 59.05 60.13 60.63 Al2O3 13.20 13.20 13.40 13.40 13.40 11.65 11.64 12.20 12.27 12.27 CaO 24.05 24.25 23.75 24.15 24.35 24.58 25.58 23.95 22.92 22.42 MgO 2.55 2.55 2.55 2.55 2.55 2.61 2.61 2.55 2.50 2.50 TiO2 1.10 1.10 1.10 1.10 1.10 1.12 1.12 1.10 1.00 1.00 Na2O 0.90 0.90 0.90 0.90 0.90 0.92 0.92 0.90 0.98 K2O 0.05 0.05 Fe2O3 0.25 0.25 0.25 0.25 0.25 0.27 0.27 0.25 0.20 0.20 SO3 0.02 0.02 SiO2/RO 2.18 2.15 2.21 2.16 2.13 2.16 2.05 2.23 2.37 2.43 T_(FORM) (° C.) 1235 1232 1240 1240 1238 1230 1222 1239 1265 1268 T_(LIQ) (° C.) 1164 1166 1167 1166 1165 1198 1215 1181 1164 1166 ΔT (° C.) 71 66 73 74 74 32 7 58 101 102 Composition Examples Weight % 11 12 13 14 15 16 17 18 19 20 SiO2 60.13 59.61 59.45 59.40 59.35 59.30 59.25 59.10 59.00 58.85 Al2O3 12.27 12.16 12.20 12.20 12.20 12.20 12.20 12.20 12.20 12.20 CaO 22.92 23.51 23.55 23.60 23.65 23.70 23.75 23.90 24.00 24.15 MgO 2.50 2.62 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 TiO2 1.00 1.00 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 Na2O 0.98 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 K2O Fe2O3 0.20 0.20 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 SO3 SiO2/RO 2.37 2.28 2.28 2.27 2.27 2.26 2.25 2.23 2.22 2.20 T_(FORM) (° C.) 1262 1251 1258 1250 1242 1248 1249 1247 1245 1242 T_(LIQ) (° C.) 1164 1170 1173 1178 1176 1180 1178 1178 1178 1186 ΔT (° C.) 98 81 85 72 66 68 71 69 67 56 Composition Examples Weight % 21 22 23 24 25 26 27 28 29 30 SiO2 59.25 59.15 58.35 58.15 58.25 57.85 57.65 58.15 57.95 57.75 Al2O3 12.40 12.60 13.20 13.20 13.40 13.40 13.40 13.20 13.20 13.20 CaO 23.55 23.45 23.65 23.85 23.55 23.95 24.15 23.85 24.05 24.25 MgO 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 TiO2 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 Na2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 K2O Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 SO3 SiO2/RO 2.27 2.28 2.23 2.20 2.23 2.18 2.16 2.20 2.18 2.15 T_(FORM) (° C.) 1253 1253 1248 1245 1244 1243 1242 1249 1246 1243 T_(LIQ) (° C.) 1171 1168 1162 1160 1174 1174 1169 1170 1171 1172 ΔT (° C.) 82 85 86 85 70 69 73 79 75 71 Composition Examples Weight % 31 32 33 34 SiO2 57.55 58.05 58.85 59.61 Al2O3 13.20 13.40 13.40 12.16 CaO 24.45 23.75 23.95 23.51 MgO 2.55 2.55 2.55 2.62 TiO2 1.10 1.10 1.10 1.00 Na2O 0.90 0.90 0.90 0.90 K2O Fe2O3 0.25 0.25 0.25 0.20 SO3 SiO2/RO 2.13 2.21 2.22 2.28 T_(FORM) (° C.) 1241 1246 1248 1251 T_(LIQ) (° C.) 1164 1163 1171 1167 ΔT (° C.) 67 83 77 84

TABLE B TYPE I-2 AND II-2 GLASS Composition Examples Weight % 35 36 37 38 39 40 41 42 43 44 SiO2 57.75 57.75 56.75 57.15 57.25 58.55 55.40 55.80 56.20 55.75 Al2O3 13.20 12.20 13.20 13.05 13.20 12.20 13.60 13.40 13.60 13.20 CaO 24.25 24.25 24.25 24.00 24.25 23.45 24.85 24.65 24.05 23.25 MgO 2.50 2.50 2.50 2.55 2.50 2.55 2.50 2.50 2.50 2.55 TiO2 1.10 1.10 1.10 1.10 1.10 1.10 0.50 0.50 0.50 1.10 Na2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 B2O3 1.00 1.00 1.00 1.00 1.00 1.00 2.00 2.00 2.00 3.00 SiO2/RO 2.16 2.16 2.12 2.15 2.14 2.25 2.03 2.06 2.12 2.16 T_(FORM) (° C.) 1240 1227 1228 1235 1239 1236 1217 1211 1219 1204 T_(LIQ) (° C.) 1178 1164 1161 1154 1159 1159 1153 1156 1136 1127 ΔT (° C.) 62 63 67 81 80 77 64 55 83 77 Composition Examples Weight % 45 46 47 48 49 50 51 52 53 54 SiO2 57.25 56.25 56.65 56.75 58.05 56.35 56.40 56.45 55.60 55.80 Al2O3 12.20 13.20 13.05 13.20 12.20 13.60 13.60 13.55 13.60 13.60 CaO 23.75 23.75 23.50 23.25 22.95 23.85 23.80 23.80 24.65 24.45 MgO 2.50 2.50 2.55 2.55 2.55 2.55 2.55 2.55 2.50 2.50 TiO2 1.10 1.10 1.10 1.10 1.10 0.50 0.50 0.50 0.50 0.50 Na2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 B2O3 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 SiO2/RO 2.18 2.14 2.17 2.20 2.28 2.13 2.14 2.14 2.05 2.07 T_(FORM) (° C.) 1227 1224 1225 1225 1225 1218 1219 1220 1211 1209 T_(LIQ) (° C.) 1148 1149 1145 1147 1142 1138 1142 1137 1154 1156 ΔT (° C.) 79 75 80 78 83 80 77 83 57 53 Composition Examples Weight % 55 56 57 58 59 60 61 62 63 64 SiO2 56.50 56.60 56.40 56.0 56.40 56.20 56.00 56.00 55.80 56.50 Al2O3 13.55 13.40 13.40 13.60 13.60 13.80 13.80 13.60 13.60 13.20 CaO 23.85 23.85 24.05 24.25 23.85 23.85 24.05 24.25 24.45 23.50 MgO 2.55 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.55 TiO2 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 1.10 Na2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 B2O3 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 SiO2/RO 2.14 2.15 2.12 2.09 2.14 2.13 2.11 2.09 2.07 2.16 T_(FORM) (° C.) 1217 1222 1216 1213 1220 1223 1219 1202 1222 1220 T_(LIQ) (° C.) 1135 1139 1143 1136 1139 1158 1151 1137 1153 1133 ΔT (° C.) 82 83 73 77 81 65 68 65 69 87 Composition Examples Weight % 65 66 67 68 69 70 71 72 73 74 SiO2 57.25 56.75 56.25 56.75 56.65 56.80 56.40 55.80 55.60 55.00 Al2O3 13.20 13.20 13.20 13.45 13.05 13.40 13.80 13.80 13.40 13.80 CaO 22.75 23.75 23.75 23.00 23.50 23.65 23.65 24.25 24.85 25.05 MgO 2.50 2.05 2.55 2.55 2.55 2.50 2.50 2.50 2.50 2.50 TiO2 1.10 1.10 1.10 1.10 1.10 0.50 0.50 0.50 0.50 0.50 Na2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 B2O3 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 SiO2/RO 2.27 2.20 2.14 2.22 2.17 2.17 2.16 2.09 2.03 2.00 T_(FORM) (° C.) 1237 1230 1220 1227 1218 1228 1197 1222 1209 1206 T_(LIQ) (° C.) 1149 1141 1131 1131 1131 1141 1156 1137 1168 1169 ΔT (° C.) 86 89 89 96 87 87 41 85 41 37 Composition Examples Weight % 75 76 77 78 79 80 81 82 83 SiO2 56.75 56.15 56.25 58.61 59.01 58.70 57.75 59.05 59.11 Al2O3 13.20 13.05 13.20 12.16 12.04 13.35 13.20 12.20 12.16 CaO 22.25 23.00 23.25 23.50 23.27 23.50 23.25 23.95 23.00 MgO 2.55 2.55 2.55 2.50 2.48 2.50 2.50 2.55 2.50 TiO2 1.10 1.10 1.10 1.10 1.09 0.50 1.10 1.10 1.10 Na2O 0.90 0.90 0.90 0.90 0.89 0.30 0.90 0.90 0.90 Fe2O3 0.25 0.25 0.25 0.23 0.23 0.25 0.25 0.25 0.23 B2O3 3.00 3.00 3.00 1.00 1.00 0.90 1.00 1.00 1.00 SiO2/RO 2.29 2.20 2.18 2.25 2.29 2.26 2.24 2.23 2.32 T_(FORM) (° C.) 1221 1212 1214 1242 1252 1253 1250 1254 1248 T_(LIQ) (° C.) 1121 1178 1114 1161 1178 1145 1154 1183 1152 ΔT (° C.) 100 34 100 81 74 108 96 71 96

TABLE C TYPE III-1 GLASS Composition Examples Weight % 84 85 86 87 88 89 90 91 92 93 SiO2 58.70 58.70 58.35 58.25 58.86 58.76 57.95 57.65 58.96 58.15 Al2O3 13.35 13.35 13.20 13.40 13.44 13.64 13.20 13.40 13.24 13.20 CaO 23.50 23.50 23.65 23.55 23.55 23.45 24.05 24.15 23.65 23.85 MgO 2.50 2.50 2.55 2.55 2.50 2.50 2.55 2.55 2.50 2.55 TiO2 0.50 0.50 1.10 1.10 0.50 0.50 1.10 1.10 0.50 1.10 Na2O 0.60 0.30 Li2O 0.60 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 SiO2/RO 2.26 2.26 2.23 2.23 2.26 2.26 2.18 2.16 2.25 2.20 T_(FORM) (° C.) 1226 1211 1211 1215 1216 1218 1205 1206 1212 1237 T_(LIQ) (° C.) 1157 1153 1146 1153 1153 1150 1151 1154 1158 1172 ΔT (° C.) 69 58 65 62 63 68 54 52 54 65 Composition Examples Weight % 94 95 96 97 98 99 100 101 102 103 SiO2 59.61 59.97 60.09 60.21 60.33 59.61 59.61 59.73 59.85 59.97 Al2O3 12.12 12.19 12.22 12.24 12.27 12.92 12.92 12.92 12.95 12.97 CaO 22.12 23.56 23.31 23.35 23.40 21.91 21.96 22.00 22.04 22.09 MgO 3.50 2.90 2.70 2.50 2.30 3.50 3.30 3.10 2.90 2.70 TiO2 0.50 0.50 0.50 0.50 0.50 1.10 1.10 1.10 1.10 1.10 Na2O Li2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 SiO2/RO 2.33 2.27 2.31 2.33 2.35 2.35 2.36 2.38 2.40 2.42 T_(FORM) (° C.) 1205 1207 1217 1213 1216 1213 1213 1214 1214 1219 T_(LIQ) (° C.) 1190 1170 1163 1162 1166 1179 1170 1164 1161 1160 ΔT (° C.) 15 37 54 51 50 34 43 50 53 59 Composition Examples Weight % 104 105 106 107 108 109 110 111 112 113 SiO2 60.09 60.21 60.00 60.57 59.80 59.75 59.65 59.60 59.55 59.50 Al2O3 13.00 13.02 12.50 13.10 12.25 12.25 12.25 12.25 12.25 12.25 CaO 22.13 22.18 23.70 22.31 22.60 22.85 23.35 23.60 23.85 24.10 MgO 2.50 2.30 1.90 1.70 3.10 2.90 2.50 2.30 2.10 1.90 TiO2 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 Na2O 0.30 0.30 0.30 0.30 0.30 0.30 Li2O 0.90 0.90 0.90 0.90 0.60 0.60 0.60 0.60 0.60 0.60 Fe2O3 0.25 0.25 0.25 0.25 SiO2/RO 2.44 2.46 2.34 2.52 2.33 2.32 2.31 2.30 2.29 2.29 T_(FORM) (° C.) 1223 1233 1239 1239 1240 1236 1236 1238 1234 1234 T_(LIQ) (° C.) 1155 1142 1139 1141 1156 1156 1159 1167 1173 1181 ΔT (° C.) 68 91 100 98 94 80 77 71 61 53 Composition Examples Weight % 114 115 116 117 118 119 120 121 122 123 SiO2 59.45 60.00 59.95 59.90 59.85 59.61 59.97 60.09 60.21 60.33 Al2O3 12.25 12.40 12.40 12.40 12.0 12.12 12.19 12.22 12.24 12.27 CaO 24.35 22.05 23.30 23.55 23.80 22.12 22.25 22.30 22.34 22.39 MgO 1.70 2.30 2.10 1.90 1.70 3.50 2.90 2.70 2.50 2.30 TiO2 1.10 1.10 1.10 1.10 1.10 1.50 1.50 1.50 1.50 1.50 Na2O 0.30 Li2O 0.60 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.25 0.25 0.26 0.25 0.25 0.25 0.25 0.25 0.25 SiO2/RO 2.28 2.46 2.36 2.35 2.35 2.33 2.38 2.40 2.42 2.44 T_(FORM) (° C.) 1234 1230 1231 1224 1224 1215 1217 1213 1215 1231 T_(LIQ) (° C.) 1192 1146 1152 1156 1156 1181 1161 1178 1162 1160 ΔT (° C.) 42 84 79 68 68 34 56 35 53 71 Composition Examples Weight % 124 125 126 127 128 129 130 131 132 133 SiO2 60.75 60.21 59.78 58.70 57.75 58.05 57.85 59.71 59.46 60.02 Al2O3 12.35 13.02 12.30 13.35 13.20 13.40 13.40 13.24 13.24 12.35 CaO 22.55 22.52 23.26 23.50 24.25 23.75 23.95 22.90 23.15 23.35 MgO 1.70 2.50 2.53 2.50 2.55 2.55 2.55 2.50 2.50 2.54 TiO2 1.50 0.50 0.50 0.50 1.10 1.10 1.10 0.50 0.50 0.50 Na2O 0.00 Li2O 0.90 1.00 1.40 1.20 0.90 0.90 0.90 0.90 0.90 1.00 Fe2O3 0.25 0.25 0.23 0.25 0.25 0.25 0.25 0.25 0.25 0.23 SiO2/RO 2.51 2.41 2.32 2.26 2.15 2.21 2.18 2.35 2.32 2.32 T_(FORM) (° C.) 1240 1231 1187 1194 1201 1202 1199 1227 1226 1209 T_(LIQ) (° C.) 1166 1143 1158 1149 1155 1153 1157 1142 1147 1159 ΔT (° C.) 74 88 29 45 46 49 42 85 79 50 Composition Examples Weight % 134 135 136 137 138 139 140 141 142 143 SiO2 59.90 60.26 60.14 59.16 60.10 60.23 60.10 60.23 59.78 60.14 Al2O3 12.32 12.40 12.37 13.24 13.00 12.25 13.00 12.25 12.30 12.37 CaO 23.31 23.45 23.40 23.45 22.15 23.36 22.15 23.36 23.26 23.40 MgO 2.53 2.55 2.54 2.50 2.50 2.50 2.50 2.50 2.53 2.54 TiO2 0.50 0.51 0.51 0.50 1.10 0.51 1.10 0.51 0.50 0.51 Na2O Li2O 1.20 0.60 0.80 0.90 0.90 0.90 0.90 0.90 1.40 0.80 Fe2O3 0.23 0.23 0.23 0.25 0.25 0.25 0.25 0.25 0.23 0.23 SiO2/RO 2.32 2.32 2.32 2.28 2.44 2.33 2.44 2.33 2.32 2.32 T_(FORM) (° C.) 1199 1230 1219 1218 1235 1220 1237 1224 1198 1219 T_(LIQ) (° C.) 1160 1158 1159 1156 1133 1160 1136 1158 1156 1159 ΔT (° C.) 39 72 60 62 102 60 101 66 42 60 Composition Examples Weight % 144 145 146 147 148 149 150 151 SiO2 60.38 60.33 59.70 60.21 60.21 60.21 60.50 58.70 Al2O3 12.42 13.05 12.25 13.02 13.02 13.02 12.45 13.35 CaO 23.50 22.22 22.85 22.52 22.52 22.52 23.54 23.50 MgO 2.55 2.10 2.70 2.50 2.50 2.50 2.56 2.50 TiO2 0.51 1.10 1.10 0.50 0.50 0.50 0.51 0.50 Na2O 0.30 0.25 0.50 0.75 0.90 Li2O 0.40 0.90 0.60 0.75 0.50 0.25 0.20 0.30 Fe2O3 0.23 0.25 0.25 0.25 0.25 0.24 0.25 SiO2/RO 2.32 2.48 2.34 2.41 2.41 2.41 2.32 2.26 T_(FORM) (° C.) 1244 1258 1242 1242 1253 1263 1256 1241 T_(LIQ) (° C.) 1158 1136 1155 1147 1152 1160 1158 1165 ΔT (° C.) 86 122 87 95 101 103 98 76 Composition Examples Weight % 152 153 154 155 156* SiO2 60.05 60.05 60.05 59.30 59.30 Al2O3 12.98 12.98 12.98 12.10 12.10 CaO 22.14 22.14 22.14 22.60 22.60 MgO 3.12 3.12 3.12 3.40 3.40 TiO2 0.55 0.55 0.55 1.50 1.50 Na2O 0.45 Li2O 0.91 0.91 0.91 0.45 0.90 Fe2O3 0.25 0.25 0.25 0.20 0.20 SiO2/RO 2.38 2.38 2.38 2.28 2.28 T_(FORM) (° C.) 1214 1219 1223 1218 1191 (NIST 710A) T_(LIQ) (° C.) 1159 1164 1163 1179 1187 ΔT (° C.) 55 55 60 39 4 * composition included 0.50 wt % BaO

TABLE D TYPE III-2 GLASS Composition Examples Weight % 157 158 159 160 161 162 163 164 165 166 SiO2 58.25 58.30 58.20 58.10 58.00 58.15 58.15 58.10 57.35 57.95 Al2O3 13.33 13.03 13.03 13.03 13.03 13.20 13.33 13.63 13.20 13.20 CaO 23.29 23.54 23.64 23.74 23.84 22.85 23.39 23.14 23.65 24.05 MgO 2.50 2.50 2.50 2.50 2.50 2.55 2.50 2.50 2.55 2.55 TiO2 0.50 0.50 0.50 0.50 0.50 1.10 0.50 0.50 1.10 1.10 Na2O Li2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 ZnO 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Fe2O3 0.23 0.23 0.23 0.23 0.23 0.25 0.23 0.23 0.25 0.25 SiO2/RO 2.26 2.24 2.23 2.21 2.20 2.29 2.25 2.26 2.19 2.18 T_(FORM) (° C.) 1213 1204 1205 1206 1208 1207 1208 1212 1195 1195 T_(LIQ) (° C.) 1146 1147 1148 1144 1149 1136 1152 1157 1141 1140 ΔT (° C.) 67 57 57 62 59 71 56 55 54 55 Composition Examples Weight % 167 168 169 170 171 172 173 174 175 176 SiO2 59.61 59.47 59.12 57.75 58.00 59.73 59.85 59.97 60.09 60.21 Al2O3 12.16 12.16 12.00 13.20 13.63 12.92 12.95 12.97 13.00 13.02 CaO 23.50 24.22 22.50 24.25 23.24 22.00 22.04 22.09 22.13 22.18 MgO 2.50 1.90 3.40 2.55 2.50 3.10 2.90 2.70 2.50 2.30 TiO2 1.10 1.10 1.00 1.10 0.50 1.10 1.10 1.10 1.10 1.10 Na2O Li2O 0.45 0.45 0.90 0.90 0.90 0.45 0.45 0.45 0.45 0.45 ZnO 0.45 0.45 1.00 1.00 1.00 0.45 0.45 0.45 0.45 0.45 Fe2O3 0.20 0.25 0.23 0.25 0.25 0.25 0.25 0.25 SiO2/RO 2.29 2.28 2.28 2.15 2.25 2.38 2.40 2.42 2.44 2.46 T_(FORM) (° C.) 1229 1218 1190 1194 1212 1242 1246 1246 1251 1251 T_(LIQ) (° C.) 1154 1159 1163 1159 1163 1173 1168 1154 1147 1144 ΔT (° C.) 75 59 27 35 49 69 78 92 104 107 Composition Examples Weight % 177 178 179 180 181 182 183 SiO2 60.33 60.45 60.57 59.40 59.20 59.54 59.40 Al2O3 13.05 13.08 13.10 12.16 12.16 12.16 12.16 CaO 22.22 22.27 22.31 23.49 23.69 23.95 24.49 MgO 2.10 1.90 1.70 2.30 2.30 2.10 1.70 TiO2 1.10 1.10 1.10 1.10 1.10 1.10 1.10 Na2O 0.40 0.40 Li2O 0.45 0.45 0.45 0.45 0.45 0.45 0.45 ZnO 0.45 0.45 0.45 0.45 0.45 0.45 0.45 Fe2O3 0.25 0.25 0.25 SiO2/RO 2.48 2.50 2.52 2.30 2.28 2.29 2.27 T_(FORM) (° C.) 1260 1260 1263 1245 1247 1241 1245 T_(LIQ) (° C.) 1140 1139 1135 1159 1152 1155 1168 ΔT (° C.) 120 121 128 86 95 86 77

TABLE E TYPE III-3 GLASS Composition Examples Weight % 184 185 186 187 188 189 190 191 192 193 SiO2 59.73 59.85 59.97 60.09 60.21 60.33 60.45 60.57 58.80 58.70 Al2O3 12.92 12.95 12.97 13.00 13.02 13.05 13.08 13.10 13.00 11.90 CaO 22.00 22.04 22.09 22.13 22.18 22.22 22.27 22.31 23.45 22.40 MgO 3.10 2.90 2.70 2.50 2.30 2.10 1.90 1.70 2.50 3.40 TiO2 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.50 ZnO 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 1.00 Na2O 0.90 K2O Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.20 SiO2/RO 2.38 2.40 2.42 2.44 2.46 2.48 2.50 2.52 2.27 2.28 T_(FORM) (° C.) 1265 1267 1273 1278 1273 1280 1285 1275 1268 1226 T_(LIQ) (° C.) 1170 1166 1159 1157 1166 1169 1170 1171 1165 1180 ΔT (° C.) 95 101 114 121 107 111 115 104 103 46 Composition Examples Weight % 194 195 196 197 SiO2 59.00 58.70 58.19 59.00 Al2O3 12.00 11.90 11.84 12.00 CaO 22.50 22.40 21.33 22.50 MgO 3.40 3.40 2.82 3.40 TiO2 1.00 1.00 1.86 1.50 ZnO 1.00 1.50 2.28 0.50 Na2O 0.90 0.90 1.18 0.90 K2O 0.16 Fe2O3 0.20 0.20 0.24 0.20 SiO2/RO 2.28 2.28 2.24 2.28 T_(FORM) (° C.) 1234 1231 1212 1230 (NIST 710A) T_(LIQ) (° C.) 1175 1181 1159 1183 ΔT (° C.) 69 50 53 37

TABLE F TYPE III-4 GLASS Composition Examples Weight % 198 199 200 201 202 203 204 205 206 207 SiO2 58.00 57.90 57.80 58.15 58.25 58.00 58.10 58.30 58.20 58.10 Al2O3 13.43 13.43 13.43 13.33 13.33 13.63 13.63 13.03 13.03 13.03 CaO 23.44 23.54 23.64 23.39 23.29 23.24 23.14 23.54 23.64 23.74 MgO 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 TiO2 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 B2O3 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Na2O K2O Li2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 SiO2/RO 2.24 2.22 2.21 2.25 2.26 2.25 2.27 2.24 2.23 2.21 T_(FORM) (° C.) 1202 1203 1197 1203 1202 1207 1212 1200 1201 1194 T_(LIQ) (° C.) 1139 1137 1139 1136 1145 1144 1146 1132 1137 1135 ΔT (° C.) 63 66 58 67 57 63 66 68 64 59 Composition Examples Weight % 208* 209* 210* 211 212 213 214 215 216 217 SiO2 58.74 58.64 58.64 58.75 58.00 57.80 57.60 57.60 57.60 57.60 Al2O3 13.05 13.15 12.95 12.93 13.03 13.23 13.23 13.23 13.23 13.03 CaO 22.97 22.97 22.87 22.93 23.84 23.84 23.84 23.84 23.84 24.04 MgO 2.36 2.36 2.36 2.36 2.50 2.50 2.50 2.50 2.50 2.50 TiO2 0.49 0.49 0.49 0.50 0.50 0.50 0.50 0.50 0.50 0.50 B2O3 1.00 1.00 1.00 1.20 1.00 1.00 1.20 1.20 1.20 1.20 Na2O 0.04 0.10 0.20 0.20 K2O 0.09 0.09 0.09 0.10 Li2O 0.91 0.91 0.91 0.90 0.90 0.90 0.90 0.80 0.70 0.70 Fe2O3 0.29 0.29 0.29 0.29 0.23 0.23 0.23 0.23 0.23 0.23 SiO2/RO 2.32 2.32 2.32 2.32 2.20 2.19 2.19 2.19 2.19 2.17 T_(FORM) (° C.) 1210 1209 1204 1210 1198 1201 1200 1196 1208 1201 T_(LIQ) (° C.) 1145 1151 1142 1127 1138 1126 1125 1133 1135 1145 ΔT (° C.) 65 58 62 83 60 75 75 63 73 56 Composition Examples Weight % 218 219 220 221 222 223 224 225 226 227 SiO2 58.50 58.40 58.30 58.40 58.15 58.25 58.70 58.00 57.60 58.00 Al2O3 12.76 12.76 13.03 13.03 13.33 13.33 12.75 13.03 13.03 13.03 CaO 23.61 23.71 23.54 23.44 23.39 23.29 23.50 23.84 24.04 23.84 MgO 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 TiO2 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 B2O3 1.00 1.00 1.00 1.00 1.00 1.00 0.60 1.00 1.20 1.00 Na2O 0.60 K2O Li2O 0.90 0.90 0.90 0.90 0.90 0.90 0.60 0.90 0.90 0.90 Fe2O3 0.23 0.23 0.23 0.23 0.25 0.25 0.25 0.23 0.23 0.23 SiO2/RO 2.24 2.23 2.24 2.25 2.25 2.26 2.26 2.20 2.17 2.20 T_(FORM) (° C.) 1202 1203 1201 1208 1197 1200 1216 1202 1194 1192 T_(LIQ) (° C.) 1141 1145 1138 1137 1130 1134 1160 1137 1142 1137 ΔT (° C.) 61 58 63 71 67 66 56 65 52 55 Composition Examples Weight % 228 229 230 231 232 233 234 235 236 237 SiO2 58.61 58.61 58.00 57.90 58.11 58.40 58.40 58.50 58.60 58.00 Al2O3 12.16 12.16 13.23 13.23 13.36 13.36 13.03 13.03 13.03 13.63 CaO 23.50 23.50 23.64 23.74 23.40 23.11 23.44 23.34 23.24 23.24 MgO 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 TiO2 1.10 1.10 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 B2O3 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Na2O 0.45 K2O Li2O 0.90 0.45 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 SiO2/RO 2.25 2.25 2.22 2.21 2.24 2.28 2.25 2.26 2.28 2.25 T_(FORM) (° C.) 1201 1227 1201 1195 1196 1204 1201 1204 1204 1206 T_(LIQ) (° C.) 1142 1159 1135 1137 1133 1133 1136 1133 1135 1136 ΔT (° C.) 59 68 66 58 63 71 65 71 69 70 Composition Examples Weight % 238 239 240 241 242 243 244 245 246 247 SiO2 58.10 58.10 58.70 58.70 58.70 58.61 58.40 58.80 58.30 57.60 Al2O3 13.23 13.43 12.75 12.35 12.35 12.16 12.76 12.46 13.03 13.03 CaO 23.54 23.34 23.50 23.50 23.50 23.50 23.71 23.61 23.54 24.04 MgO 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 TiO2 0.50 0.50 0.50 0.50 0.50 1.10 0.50 0.50 0.50 0.50 B2O3 1.00 1.00 0.60 1.00 1.00 1.00 1.00 1.00 1.00 1.20 Na2O 0.30 0.60 0.30 0.10 K2O Li2O 0.90 0.90 0.90 0.60 0.90 0.90 0.90 0.90 0.90 0.80 Fe2O3 0.23 0.23 0.25 0.25 0.25 0.23 0.23 0.23 0.23 0.23 SiO2/RO 2.23 2.25 2.26 2.26 2.26 2.25 2.23 2.25 2.24 2.17 T_(FORM) (° C.) 1199 1204 1204 1207 1202 1194 1194 1195 1195 1196 T_(LIQ) (° C.) 1133 1134 1153 1157 1149 1141 1144 1145 1140 1145 ΔT (° C.) 63 70 51 50 53 53 50 50 55 51 Composition Examples Weight % 248 249 250 251 252 253 254 255 256 257 SiO2 58.50 58.11 58.91 58.11 58.30 58.20 58.10 58.70 58.70 58.11 Al2O3 12.76 13.36 12.16 13.36 13.03 13.03 13.03 13.35 13.35 13.36 CaO 23.61 23.40 23.80 23.40 23.54 23.64 23.74 23.50 23.50 23.40 MgO 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 TiO2 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 B2O3 1.00 1.00 1.00 1.00 1.00 1.00 1.00 0.30 0.60 1.00 Na2O K2O Li2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.60 0.90 Fe2O3 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.25 0.25 0.23 SiO2/RO 2.24 2.24 2.24 2.24 2.24 2.23 2.21 2.26 2.26 2.24 T_(FORM) (° C.) 1197 1229 1216 1213 1202 1202 1205 1207 1224 1212 T_(LIQ) (° C.) 1139 1155 1148 1142 1136 1136 1137 1144 1145 1135 ΔT (° C.) 58 133 123 126 120 119 122 114 142 139 Composition Examples Weight % 258 259 260 261 262 263 264 265 266 267 SiO2 58.20 58.70 59.53 59.61 59.11 59.11 59.16 59.21 57.80 59.11 Al2O3 13.23 12.35 12.25 12.16 12.16 12.16 12.16 12.16 13.03 12.16 CaO 23.44 23.50 23.17 23.50 23.00 23.00 23.20 23.40 24.04 23.50 MgO 2.50 2.50 2.52 2.50 2.50 2.50 2.25 2.00 2.50 2.00 TiO2 0.50 0.50 0.50 1.10 1.10 1.10 1.10 1.10 0.50 1.10 B2O3 1.00 1.00 1.00 0.45 1.00 1.00 1.00 1.00 1.00 1.00 Na2O K2O Li2O 0.90 1.20 0.80 0.45 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.23 0.25 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 SiO2/RO 2.24 2.26 2.32 2.29 2.32 2.32 2.32 2.33 2.18 2.32 T_(FORM) (° C.) 1204 1187 1214 1230 1205 1216 1218 1213 1196 1209 T_(LIQ) (° C.) 1135 1147 1143 1155 1142 1143 1147 1153 1147 1153 ΔT (° C.) 124 40 71 75 63 73 71 60 49 56 Composition Examples Weight % 268 269 270 271 272 273 274 275 276 277 SiO2 59.36 59.31 59.36 59.41 59.11 59.16 59.21 59.16 59.11 59.01 Al2O3 12.41 12.56 12.51 12.46 12.16 12.16 12.16 12.26 12.26 12.36 CaO 23.60 23.50 23.50 23.50 23.00 23.20 23.40 23.45 23.50 23.50 MgO 2.00 2.00 2.00 2.00 2.50 2.25 2.00 2.50 2.50 2.50 TiO2 0.50 0.50 0.50 0.50 1.10 1.10 1.10 0.50 0.50 0.50 B2O3 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Na2O K2O Li2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Fe2O3 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 SiO2/RO 2.32 2.33 2.33 2.33 2.32 2.32 2.33 2.28 2.27 2.27 T_(FORM) (° C.) 1216 1220 1220 1220 1216 1214 1220 1209 1210 1210 T_(LIQ) (° C.) 1153 1153 1158 1155 1144 1147 1158 1150 1152 1152 ΔT (° C.) 63 67 62 65 72 67 62 59 58 58 Composition Examples Weight % 278 279 280 281 282 283 284 285 286 287 SiO2 58.91 58.91 59.21 58.31 58.61 58.70 58.60 58.50 58.75 58.75 Al2O3 12.36 12.16 12.16 12.16 12.76 12.46 12.46 12.46 12.93 12.93 CaO 23.60 23.80 23.50 24.40 23.50 23.71 23.81 23.91 22.93 22.93 MgO 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.36 2.36 TiO2 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 B2O3 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.20 1.20 Na2O 0.14 0.24 K2O 0.10 0.10 Li2O 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.80 0.70 Fe2O3 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.29 0.29 SiO2/RO 2.26 2.28 2.28 2.17 2.25 2.24 2.23 2.22 2.32 2.32 T_(FORM) (° C.) 1196 1196 1201 1195 1183 1193 1192 1191 1211 1218 T_(LIQ) (° C.) 1152 1156 1143 1151 1165 1152 1151 1152 1127 1129 ΔT (° C.) 44 40 58 44 18 41 41 39 84 89 Composition Examples Weight % 288 289 290 291 292 293 294 295 296 297 298 SiO2 58.50 58.70 58.70 58.10 58.70 58.91 59.11 59.31 59.21 60.12 59.11 Al2O3 12.34 13.05 12.75 13.63 13.35 12.16 12.16 12.26 12.26 13.00 12.16 CaO 23.70 23.50 23.50 23.14 23.50 23.80 23.50 22.30 23.40 21.13 23.00 MgO 2.50 2.50 2.50 2.50 2.50 2.50 2.00 2.50 2.50 2.50 2.50 TiO2 0.50 0.50 0.50 0.50 0.50 0.50 1.10 0.50 0.50 1.10 1.10 B2O3 1.20 0.30 0.60 1.00 0.90 1.00 1.00 1.00 1.00 1.00 1.00 Na2O 0.45 K2O 0.08 LiO2 0.90 .20 1.20 0.90 0.30 0.90 0.90 0.90 0.90 0.90 0.45 Fe2O3 0.28 0.25 0.25 0.23 0.25 0.23 0.23 0.23 0.23 0.25 0.23 SiO2/RO 2.23 2.26 2.26 2.27 2.26 2.24 2.32 2.39 2.29 2.54 2.32 T_(FORM) (° C.) 1195 1196 1195 1204 1239 1197 1215 1209 1210 1285 1243 T_(LIQ) (° C.) 1151 1147 1147 1115 1143 1155 1155 1148 1156 1189 1149 ΔT (° C.) 44 49 48 89 96 42 60 61 54 96 94 * compositions include 0.05 wt % SrO and 0.08 wt % SO3

The samples were experimental samples produced in a laboratory. The experimental samples were prepared from reagent grade oxides (e.g., pure silica or calcia). The batch size for each example was 1000 grams. The individual batch ingredients were weighed out, combined and placed in a tightly sealed glass jar or plastic container. The sealed jar or container was then placed in a paint shaker for 15 minutes or in a turbular mixer for 25 minutes to effectively mix the ingredients. A portion of the batch was then place into a platinum crucible, filling no more than ¾ of its volume. The crucible was then placed in a furnace and heated to 1427° C. (2600° F.) for 15 minutes. The remaining batch was then added to the hot crucible and heated to 1427° C. (2600° F.) for 15 to 30 minutes. The furnace temperature was then raised to 1482° C. (2700° F.) and held there for 2 hours. The molten glass was then fritted in water and dried. The fritted samples were remelted at 1482° C. (2700° F.) and held there for 2 hours. The molten glass was then fritted again in water and dried. The forming temperature, i.e. the glass temperature at a viscosity of 1000 poise, was determined by ASTM method C965-81, and the liquidus temperature by ASTM method C829-81.

The weight percent of the constituents of the compositions shown in Tables A through F are based on the weight percent of each constituent in the batch. It is believed that the batch weight percent is generally about the same as the weight percent of the melted sample, except for glass batch materials that volatilize during melting, e.g. boron and fluorine. For boron, it is believed that the weight percent of B₂O₃ in a laboratory sample will be 5 to 15 percent less than the weight percent of B₂O₃ in the batch composition, the precise loss depending on the composition and melting conditions. For fluorine, It is believed that the weight percent of fluorine in a laboratory test sample will be about 50 percent less than the weight percent of fluorine in the batch composition, the precise loss depending on the composition and melting conditions. It is further believed that glass fiber compositions made from commercial grade materials and melted under conventional operating conditions will have similar batch and melt weight percents as discussed above, with the precise loss depending, in part, on the furnace operating temperature, through-put and quality of commercial batch materials. The amount of born and fluorine reported in the tables takes into consideration the expected loss of these materials and represents the expected amount of the material in the glass composition.

Determination of the log 3 forming temperature was based on the glass samples being compared against physical standards supplied by the National Institute of Standards and Testing (NIST). In Tables A through F, the reported log 3 forming temperature is based on comparison to either NIST 710A or NIST 714, both of which are a soda lime silica glass standard. It is expected that both standards will provide comparable results since both are based on a soda lime silica standard. The T_(LIQ) is unaffected by the NIST standard. Unless otherwise stated, the log 3 forming temperatures reported herein are based on the NIST 714 standard.

In the present invention, the compositional variables of interest are the weight percent SiO₂ and weight percent RO, and the relationship of interest is the ratio of SiO₂ to RO, i.e. SiO₂/RO. The melt properties of interest are the forming temperature and the liquidus temperature since one goal in the present invention is to provide a low boron glass composition having a lowered forming temperature and a desired ΔT so that the composition can be processed at a lowered temperature while reducing the possibility of devitrification of the molten glass in the bushing area during a glass fiber forming operation. Without limiting the present invention, in one nonlimiting embodiment, the glass composition has a ΔT of at least 50° C. (90° F.), e.g. at least 55° C. (100° F.). In other nonlimiting embodiments, the glass composition has a ΔT of 50 to 100° C. (90 to 180° F.), or 50 to 83° C. (90 to 150° F.), or 50 to 72° C. (90 to 130° F.).

Referring to FIGS. 1 through 6, the relationship between the SiO₂/RO ratio is plotted against both the forming temperature and liquidus temperature of the sample. The most suitable trendlines for the temperatures are based on a second order regression analysis protocol, and in particular are 2nd order polynomial curves generated using Microsoft® Excel 97 SR-2(f). By inference, both trendlines also show the resulting change of the ΔT between liquidus and forming temperatures.

In viewing FIGS. 1 through 6, it can be seen that as the SiO₂/RO ratio decreases, the forming temperature generally decreases, while the trend in the liquidus temperature differs depending on the glass type. In addition, it can be seen that as the SiO₂/RO ratio decreases, ΔT also decreases. As a result, the SiO₂/RO ratio can be used to reduce the forming temperature of a glass fiber forming composition while providing a desired ΔT. More particularly, in the present invention where ΔT is at least 50° C., a composition having a ΔT of 50° C. is indicative of a composition having a combination of materials and amounts that provides a minimum permissible forming temperature, i.e. the lowest forming temperature for the particular combination of constituents that still maintains the desired range between the forming and liquidus temperatures. From this, it can be inferred that the narrower the ΔT range, the closer the glass forming temperature is to having the minimum permissible forming temperature for that particular combination of constituents. It can also be inferred that the further the ΔT of a glass composition is from the minimum permissible ΔT, the greater the opportunity to modify the glass composition in a manner that reduces T_(FORM) while maintaining a ΔT no less than the minimum permissible ΔT. To this end, the SiO₂/RO ratio can be manipulated by changing the amount of SiO₂ and/or RO to produce a glass composition having a ΔT as close as possible to the minimum desired ΔT. It should be appreciated that if the SiO₂/RO ratio drops too low, ΔT can drop to an unacceptable level. Although not required, in one nonlimiting embodiment of the present invention, SiO₂/RO is no greater that 2.35. In other nonlimiting embodiments, SiO₂/RO is no greater than 2.30, or no greater than 2.25, or no greater than 2.20. In still another nonlimiting embodiment of the invention, SiO₂/RO ranges from 1.9 to 2.3, e.g. 2.05 to 2.29.

Although Tables A through F and corresponding FIGS. 1 through 6 illustrate how the ratio of the weight percent of SiO₂ to RO effects the melt properties of the glass, and in particular the liquidus temperature, forming temperature and ΔT, additional glass sample compositions as well as additional relationships between the glass constituents, such as for example the difference in the amount of SiO₂ and RO (i.e. SiO₂ wt %-RO wt %), the weight percent of Al₂O₃, the ratio of SiO₂ to Al₂O₃, and the ratio of RO to Al₂O₃, as they relate to liquidus and forming temperatures and ΔT, are disclosed in U.S. Provisional Application No. 60/230474, which is incorporated herein by reference.

It is known that pure silica is the highest melting glass former. A pure silica melt does not have a well defined melting point, but gradually solidifies and forms a glass as it cools to room temperature and its viscosity drops from greater than log 4 (10,000) poise at 2500° C. (1371° F.). Pure calcia, magnesia and alumina melts are known to have very low viscosities of 0.5-2 poise at their respective melting points. These materials do not solidify into a glass but rather crystallize instantly at their sharply defined melting point. In a typical quaternary SiO₂—Al₂O₃—CaO—MgO glass composition with 60% SiO₂ and 21% CaO, each oxide contributes its unique characteristics toward its balance of melt properties.

Based on these material properties, it can be inferred that as SiO₂, which is the largest oxide component of the glass composition in terms of weight percent, is reduced in a given composition of this type, the melt viscosity and the resulting log 3 forming temperature drops. If CaO, which is the second largest component of the glass composition in terms of weight percent, is increased in such a composition, the effect of RO (CaO+MgO) on the glass properties will be twofold. More specifically, it will not only increase the fluidity of the resulting melt (i.e. decrease its viscosity) but it will also increase the crystallizability of the resulting melt (i.e. increase its liquidus temperature), and therefore reduce the ΔT.

As a result, although not required, in one nonlimiting embodiment of the present invention, the glass compositions have (1) the lowest SiO₂ content that will yield the lowest log 3 forming temperatures, in combination with (2) the ratio of SiO₂ to RO (RO═CaO+MgO) that yields the process-required ΔT, which in the present invention is at least 50° C.

Based on the above and although not required, in one nonlimiting embodiment of the present invention, the silica, level is kept low, i.e. no greater than 59 wt % SiO₂, in order to promote a lower log 3 forming temperature. In other nonlimiting embodiments of the present invention, the glass compositions have no greater than 58 wt % SiO₂, or no greater than 57 wt % SiO₂.

Table G summarizes features of selected low boron glass compositions disclosed in Tables A through F that have (i) a T_(FORM) of no greater than 1240° C. (2264° F.), (ii) a ΔT in the range of 50-83° C. (90-150° F.) and (iii) no greater than 59 wt % SiO₂. It has been found that a forming temperature of greater than 1240° C. can accelerate the precious metal loss in the glass fiber forming bushings. In other nonlimiting embodiments of the present invention, the forming temperature is no greater than 1230° C., or no greater than 1220° C., or no greater than 1210° C., or no greater than 1200° C.

For comparison purposes, Table G also includes similar features of selected Type I-1 and I-2 glasses, two commercial boron containing E-glass compositions, and two commercial ADVANTEX glass compositions. It is noted that none of these specific examples meets the selection criteria for the glasses of the present invention presented in Table G.

TABLE G Composition % SiO₂ SiO₂/RO T_(FORM) (° C.) T_(LIQ) (° C.) ΔT (° C.) commercial glass 1¹ 55.2 2.31 1207 1069 138 (5.1 wt % B₂O₃) commercial glass 2¹ 53.1 2.32 1172 1077 95 (6.1 wt % B₂O₃) Type I-1 glass (no boron) from Patent '106 59 2.27 1249² 1149 100 from Patent '144 - Ex. 1 60.18 2.46 1255² 1180 75 from Patent '329 59.05-60.08 2.18-2.43 1248-1289² 1169-1219 56-96 commercial ADVANTEX 59.36 2.26 1268 1180 88 glass sample 1³ commercial ADVANTEX 60.17 2.28 1266 1189 77 glass sample 2³ Type I-2 glass from Patent '144 - Ex. 2 60.82 2.53 1262² 1180 82 (1.8 wt % B₂O₃) Selection criteria ≦59 ≦1240 50-83 Type II-I (no boron) 57.45-58.05 2.13-2.21 1232-1240 1164-1167 66-74 Type II-2 (w/B₂O₃) 55.4-58.55 2.03-2.28 1202-1240 1127-1178 55-83 Type III-1 (no boron) 57.65-58.96 2.16-2.26 1205-1237 1146-1172 52-69 Type III-2 (no boron) 57.35-58.30 2.18-2.29 1195-1213 1136-1157 54-71 Type III-3 (no boron) 58.19-59.00 2.24-2.28 1212-1234 1159-1181 50-69 Type III-4 (w/B₂O₃) 57.60-58.80 2.17-2.32 1192-1227 1125-1160 50-83 ¹produced by PPG Industries, Inc., Pittsburgh, PA. ²glass standard unknown ³sample analyzed using X-ray fluorescence analysis

Referring to Table G, it can be seen that the selected boron-free Type II-1, III-1, III-2 and III-3 glasses generally have less SiO₂, a lower SiO₂/RO ratio, a lower forming temperature, and a narrower ΔT range than the sample boron-free Type I-1 glasses. Similarly, the selected boron-containing Type II-2 and III-4 glasses generally have less SiO₂, a lower SiO₂/RO ratio, a lower forming temperature, and a narrower ΔT range than the sample boron-containing Type I-2 glasses. Furthermore, the selected Type II and III glasses generally have a higher SiO₂ content, a lower SiO₂/RO ratio, and a narrower ΔT range than the two commercial, high boron content samples.

Tables H, I, J and K illustrate additional glass compositions according to the present invention.

TABLE H Composition Examples Weight % 299 300 301 302 303 304 305 306 307 308 309 SiO2 56.25 56.45 56.75 56.50 56.75 57.5 56.75 57.75 57.75 57.75 55.40 Al2O3 13.2 13.20 13.20 13.20 13.20 12.2 13.2 12.2 12.2 12.2 13.6 CaO 24.25 24.25 23.95 24.00 23.75 24 23.95 23.75 23.75 23.95 24.5 MgO 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.95 TiO2 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 Na2O 0.9 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.45 K2O 0.45 Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 B2O3 1.30 1.30 1.30 1.30 1.40 1.30 1.20 1.40 1.30 1.40 1.30 SiO2/RO 2.10 2.11 2.14 2.13 2.16 2.17 2.14 2.20 2.20 2.18 2.02 T_(FORM) (° C.) 1210 1214 1215 1215 1215 1216 1216 1217 1217 1218 1210 T_(LIQ) (° C.) 1154 1159 1154 1154 1160 1152 1147 1151 1147 1155 1157 ΔT (° C.) 56 55 61 61 55 64 69 66 70 63 53 Composition Examples Weight % 310 311 312 313 314 315 316 317 318 319 320 SiO2 55.40 56.05 55.85 56.00 56.60 56.50 56.10 56.50 55.95 56.50 56.45 Al2O3 13.60 13.10 13.38 13.37 13.25 13.45 13.38 13.45 13.95 13.49 13.48 CaO 24.50 24.55 24.67 24.53 24.60 24.50 24.42 24.50 24.55 24.46 24.52 MgO 2.95 2.75 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 TiO2 1.10 1.10 1.10 1.10 0.55 0.55 0.55 0.55 0.55 0.55 0.55 Na2O 0.45 0.45 0.45 0.45 0.90 0.90 0.90 0.90 0.90 0.90 0.90 K2O 0.45 0.45 0.45 0.45 Fe2O3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 B2O3 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 SiO2/RO 2.02 2.05 2.05 2.07 2.09 2.09 2.08 2.09 2.07 2.09 2.09 T_(FORM) (° C.) 1211 1218 1220 1221 1211 1212 1215 1215 1216 1218 1219 T_(LIQ) (° C.) 1151 1156 1148 1157 1153 1158 1150 1157 1162 1161 1158 ΔT (° C.) 60 62 72 64 58 54 65 58 54 57 61

TABLE I Composition Examples Weight % 312 322 323 324 325 326 327 328 329 330 331 332 SiO2 55.50 55.25 55.00 55.75 55.50 55.25 54.20 54.50 54.12 55.00 54.50 54.70 Al2O3 13.20 13.20 13.20 13.30 13.30 13.30 13.35 13.25 13.30 13.25 13.25 13.20 CaO 23.50 23.75 24.00 23.70 23.95 24.20 24.55 24.55 24.55 24.25 24.55 24.50 MgO 2.55 2.55 2.55 2.55 2.55 2.55 2.55 2.55 3.00 2.55 2.67 2.55 TiO2 1.10 1.10 1.10 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 Na2O 0.90 0.90 0.90 0.90 0.90 0.90 0.45 0.45 0.45 0.45 0.45 0.45 K2O 0.55 0.55 0.55 0.55 0.55 0.55 B2O3 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Fe2O3 0.250 0.250 0.250 0.250 0.250 0.250 0.28 0.28 0.28 0.28 0.28 0.28 F 0.20 0.20 0.10 0.10 0.10 0.10 SrO 0.12 0.12 0.10 0.12 0.10 0.12 SiO2/RO 2.13 2.10 2.07 2.12 2.09 2.07 1.99 2.01 1.96 2.05 2.00 2.02 T_(FORM) (° C.) 1193 1198 1201 1201 1200 1198 1190 1194 1196 1197 1201 1201 T_(LIQ) (° C.) 1129 1122 1127 1127 1129 1128 1120 1124 1132 1124 1131 1119 ΔT (° C.) 64 76 74 74 71 70 70 70 64 73 70 82

TABLE J Composition Examples Weight % 333 334 335 336 SiO2 53.05 53.50 53.00 53.00 Al2O3 14.01 14.00 13.50 13.10 CaO 24.28 24.00 24.00 24.00 MgO 1.00 1.50 2.50 2.90 TiO2 0.52 0.50 0.50 0.50 Na2O 0.53 0.90 0.90 0.90 Fe2O3 0.91 0.10 0.10 0.10 B2O3 5.10 4.94 4.93 5.02 K2O 0.10 0.37 0.37 0.37 F 0.52 0.50 0.50 0.50 SrO 0.13 0.13 0.13 0.13 Cr2O3 0.13 0.13 0.13 SiO2/RO 2.01 2.10 2.00 1.97 T_(FORM) (° C.) 1171 1177 1172 1167 T_(LIQ) (° C.) 1114 1122 1103 1110 ΔT (° C.) 57 57 69 57

TABLE K Composition Examples Weight % 337 338 339 SiO2 54.60 56.75 57.85 Al2O3 13.35 13.20 12.45 CaO 24.55 23.95 24.05 MgO 2.55 2.55 2.55 TiO2 0.35 1.10 0.55 Na2O 0.15 0.60 0.60 Fe2O3 0.28 0.25 0.35 B2O3 3.00 1.40 1.30 K2O 0.55 F 0.20 SrO 0.12 Li2O 0.30 0.30 0.30 SiO2/RO 2.19 2.27 2.35 T_(FORM) (° C.) 1187 1206 1208 T_(LIQ) (° C.) 1133 1152 1154 ΔT (° C.) 54 54 54

More particularly, the compositions in Table H are Type II-2 glass compositions, i.e. low boron content glasses having 1.2 to 1.4 wt % B₂O₃, which have a low SiO₂ content ranging from 55.4 to 57.75 wt %, a SiO₂/RO ratio ranging from 2.02 to 2.20, a forming temperature ranging from 1210 to 1221° C. and a ΔT ranging from 54 to 72° C. Table I compositions are also low boron Type II-2 compositions the include 3 wt % B₂O₃. These compositions have a low SiO₂ content ranging from 54.12 to 55.75 wt %, a SiO₂/RO ratio ranging from 1.96 to 2.13, a forming temperature ranging from 1193 to 1201° C. and a ΔT ranging from 64 to 82° C. Table J includes additional Type II-2 compositions having a B₂O₃ of around 5 wt %. Of particular note for the compositions in Table J are the low SiO₂ contents (53.00 to 53.50 wt %), SiO₂/RO ratios (1.97 to 2.10), forming temperatures (1167 to 1177° C.), and ΔT range (57 to 69° C.). Table K includes Type III-4 compositions that have a low SiO₂ content ranging from 54.60 to 57.85 wt %, a SiO₂/RO ratio ranging from 2.19 to 2.35, a forming temperature ranging from 1187 to 1208° C. and a ΔT of 54° C.

Based on the above, in one nonlimiting embodiment of the present invention, the glass fiber composition comprises 52 to 62 percent by weight SiO₂, 0 to 2 percent by weight Na₂O, 16 to 25 percent by weight CaO, 8 to 16 percent by weight Al₂O₃, 0.05 to 0.80 percent by weight Fe₂O₃, 0 to 2 percent by weight K₂O, 1 to 5 percent by weight MgO, 0 to 5 percent by weight B₂O₃, 0 to 2 percent by weight TiO₂, and 0 to 1 percent by weight F, wherein the glass composition has a log 3 forming temperature of no greater than 1240° C. based on an NIST 714 reference standard, a ΔT of at least 50° C., and a SiO₂/RO ratio of no greater than 2.35. In another nonlimiting embodiment, the SiO₂ content of the glass composition is no greater than 59 percent by weight, ΔT is in the range from 50 to 83° C., and the SiO₂/RO ratio is in the range from 1.9 to 2.3, and further the log 3 forming temperature is no greater than 1230° C. based on an NIST 714 reference standard. In still another nonlimiting embodiment, the glass composition is boron-free.

In another nonlimiting embodiment of the present invention, the glass fiber composition comprises 53 to 59 percent by weight SiO₂, 0 to 2 percent by weight Na₂O, 16 to 25 percent by weight CaO, 8 to 16 percent by weight Al₂O₃, 0.05 to 0.80 percent by weight Fe₂O₃, 0 to 2 percent by weight K₂O, 1 to 4 percent by weight MgO, 0 to 5 percent by weight B₂O₃, 0 to 2 percent by weight TiO₂, and 0 to 1 percent by weight F, wherein the glass composition has a log 3 forming temperature of no greater than 1240° C. based on an NIST 714 reference standard, a ΔT in the range of 50 to 100° C., and a SiO₂/RO ratio in the range of 1.9 to 2.3.

In viewing the tables and figures, it should be appreciated that many of the sample compositions, although they have a ΔT greater than the minimum required ΔT for a particular process, they also have a higher forming temperature than that of the compositions of the present invention due, in part, to their high silica levels and/or high SiO₂/RO ratios. As a result, such compositions are more expensive to produce commercially, at least in terms of energy costs. Such compositions include the Type I compositions discussed herein. In addition, the tables and figures contain many samples containing a ΔT less than the minimum desired ΔT of 50° C. (90° F.). These types of compositions can be found across the compositional spectrum in each figure but especially at low silica and SiO₂/RO levels. Because of the narrower ΔT range, the risk of the molten glass solidifying in the bushing area during a glass fiber forming operation increases to an unacceptable level.

It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications that are within the spirit and scope of the invention, as defined by the appended claims. 

I claim:
 1. A glass composition comprising: SiO₂  57 to 60.8 percent by weight; Al₂O₃  12 to 13.6 percent by weight; CaO  22 to 25 percent by weight; MgO 1.7 to 3 percent by weight; TiO₂ 0.5 to 2 percent by weight; Li₂O 0.6 to 1.5 percent by weight; Na₂O   0 to 2 percent by weight; K₂O   0 to 2 percent by weight; Fe₂O₃  up to 0.5 percent by weight;

wherein the glass composition is essentially boron-free, has a log 3 forming temperature no greater than 1230° C. based on NIST 710A reference standard, the difference between the log 3 forming temperature and the liquidus temperature is at least 50° C., and the ratio of SiO₂ to (CaO+MgO) is no greater than 2.42.
 2. The glass composition according to claim 1, wherein the glass is essentially fluorine-free.
 3. The glass composition according to claim 1, wherein the ratio of SiO₂ to (CaO+MgO) is no greater than 2.40.
 4. The glass composition according to claim 1, wherein the ratio of SiO₂ to (CaO+MgO) is from 2.15 to 2.35.
 5. The glass composition according to claim 1, wherein the glass composition has a log 3 forming temperature no greater than 122020 C. based on an NIST 714 reference standard.
 6. The glass composition according to claim 2, wherein the difference between the log 3 forming temperature and the liquidus temperature is at least 60° C.
 7. The glass composition according to claim 5, wherein the difference between the log 3 forming temperature and the liquidus temperature is at least 60° C.
 8. A glass composition comprising: SiO₂   59 to 60.2 percent by weight; Al₂O₃ 12.2 to 13.2 percent by weight; CaO   23 to 25 percent by weight; MgO   2 to 2.5 percent by weight; TiO₂  0.5 to 1.5 percent by weight; Li₂O  0.8 to 1 percent by weight; Na₂O   0 to 1 percent by weight; K₂O   0 to 1 percent by weight; Fe₂O₃  up to 0.5 percent by weight;

wherein the glass composition is essentially boron-free, has a log 3 forming temperature no greater than 1230° C. based on NIST 710A reference standard, the difference between the log 3 forming temperature and the liquidus temperature is at least 50° C., and the ratio of SiO₂ to (CaO+MgO) is no greater than 2.42.
 9. The glass composition according to claim 8, wherein the log 3 forming temperature is no greater than 1220° C.
 10. The glass composition according to claim 8, wherein the difference between the log 3 forming temperature and the liquidus temperature is at least 60° C. 